Lubricant compositions for direct injection engines

ABSTRACT

The disclosed technology provides a lubricating composition and a method of lubricating an internal combustion engine where the lubricating composition contains an oil of lubricating viscosity, one or more metal-containing, sulfur-free, alkyl-phenol based detergents, an alkaline earth metal sulfonate detergent, a polyisobutenyl succinimide dispersant, and a dispersant viscosity modifier having a number average molecular weight of at least 20,000. The lubricating composition of the present invention can be formulated to have lower HTHS viscosity, and reduced phosphorous content, while providing protection against adhesive wear.

FIELD OF INVENTION

The disclosed technology relates to lubricants, particularly forinternal combustion engines including diesel engines. In particular, thedisclosed technology relates to lower viscosity lubricating compositionswhich provide improved protection against adhesive wear.

BACKGROUND OF THE INVENTION

A common wear issue in internal combustion engines is adhesive wear,also known as stick-tear wear. Adhesive wear occurs when material fromtwo mated metal parts is transferred unevenly from one part to the otherdue to a lubricant's inability to maintain separation of the two partsor inability to maintain a low enough temperature in the system. Inthese cases, the mated parts develop micro-welds which are then tornaway as the two parts move away from each other. Adhesive wear is oftenaddressed by increasing the viscosity of the lubricant and/or byincreasing the amount of anti-wear additives in the lubricatingcomposition.

Certain lubricating compositions, such as crankcase lubricants, arebeing formulated with lower high temperature high shear (HTHS)viscosities in order to improve fuel economy. In addition, somelubricating compositions are being formulated with lower levels ofanti-wear additives, in particular, phosphorous or sulfur containinganti-wear additives, for environmental reasons. However, the reductionin HTHS viscosity and/or anti-wear additives generally causes anincrease in adhesive wear on the metal to metal surfaces.

Therefore, there exists a need for a lower HTHS viscosity lubricantwhich is still able to provide protection from adhesive wear. Inaddition, there exists a need for lubricating compositions containinglower levels of phosphorous or sulfur that maintain adequate adhesivewear performance.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is directed to a lubricatingcomposition comprising an oil of lubricating viscosity, one or moremetal-containing sulfur-free detergents derived from an alkylphenol inan amount to deliver at least 0.2 weight percent alkylphenol-containingsoap to the composition, one or more alkaline earth metal sulfonatedetergents in an amount to deliver at least 0.8% by weight sulfonatesoap to the composition, 1 wt % to 4.5 wt % of one or morepolyisobutenyl succinimide dispersants, and 0.1 wt % to 1.2 wt % of adispersant viscosity modifier derived from a polyolefin having a numberaverage molecular weight of at least 20,000, wherein the lubricantcomposition contains less than 0.2 wt % of a sulfur-coupled phenatedetergent.

In another embodiment, the present invention is directed to a method oflubricating a compression ignition internal combustion engine comprisingsupplying to the engine a low phosphorus lubricant compositioncomprising an oil of lubricating viscosity, one or more metal-containingsulfur-free detergents derived from an alkylphenol in an amount todeliver at least 0.2 weight percent alkylphenol-containing soap to thecomposition, one or more alkaline earth metal sulfonate detergents in anamount to deliver at least 0.8% by weight sulfonate soap to thecomposition, 1 wt % to 4.5 wt % of one or more polyisobutenylsuccinimide dispersants, and 0.1 wt % to 1.2 wt % of a dispersantviscosity modifier derived from a polyolefin having a number averagemolecular weight of at least 20,000, wherein the lubricant compositioncontains less than 0.2 wt % of a sulfur-coupled phenate detergent.

In another embodiment, the present invention is directed to a method ofreducing adhesive wear in a compression engine lubricated with a lowphosphorus lubricant composition, comprising supplying to the engine alubricant composition comprising an oil of lubricating viscosity, one ormore metal-containing sulfur-free detergents derived from an alkylphenolin an amount to deliver at least 0.2 weight percentalkylphenol-containing soap to the composition, one or more alkalineearth metal sulfonate detergents in an amount to deliver at least 0.8%by weight sulfonate soap to the composition, 1 wt % to 4.5 wt % of oneor more polyisobutenyl succinimide dispersants, and 0.1 wt % to 1.2 wt %of a dispersant viscosity modifier derived from a polyolefin having anumber average molecular weight of at least 20,000, wherein thelubricant composition contains less than 0.2 wt % of a sulfur-coupledphenate detergent.

DETAILED DESCRIPTION OF THE INVENTION

The disclosed technology provides a lubricating composition and a methodfor lubricating an internal combustion engine. The lubricatingcomposition of the present invention comprises an oil of lubricatingviscosity, one or more metal-containing sulfur-free detergents derivedfrom an alkylphenol in an amount to deliver at least 0.2 weight percentalkylphenol-containing soap to the composition, 1 wt % to 4.5 wt % ofone or more polyisobutenyl succinimide dispersants, one or more alkalineearth metal sulfonate detergents in an amount to deliver at least 0.8%by weight sulfonate soap to the composition, and 0.1 wt % to 1.2 wt % ofa dispersant viscosity modifier derived from a polyolefin having anumber average molecular weight of at least 20,000, wherein thelubricant composition contains less than 0.2 wt % of a sulfur-coupledphenate detergent. Information about the components and other details ofthe lubricating composition of the invention are described below.

Oils of Lubricating Viscosity

The lubricating composition comprises an oil of lubricating viscosity.Such oils include natural and synthetic oils, oil derived fromhydrocracking, hydrogenation, and hydrofinishing, unrefined, refined andre-refined oils and mixtures thereof. The various types of oils oflubricating viscosity are described herein below and may be used in thelubricating composition of the present invention.

Unrefined oils are those obtained directly from a natural or syntheticsource generally without (or with little) further purificationtreatment.

Refined oils are similar to the unrefined oils except they have beenfurther treated in one or more purification steps to improve one or moreproperties. Purification techniques are known in the art and includesolvent extraction, secondary distillation, acid or base extraction,filtration, percolation and the like.

Re-refined oils are also known as reclaimed or reprocessed oils, and areobtained by processes similar to those used to obtain refined oils andoften are additionally processed by techniques directed to removal ofspent additives and oil breakdown products.

Natural oils useful in making the inventive lubricants include animaloils, vegetable oils (e.g., castor oil), mineral lubricating oils suchas liquid petroleum oils and solvent-treated or acid-treated minerallubricating oils of the paraffinic, naphthenic or mixedparaffinic-naphthenic types and oils derived from coal or shale ormixtures thereof.

Synthetic lubricating oils are useful and include hydrocarbon oils suchas polymerised and interpolymerised olefins (e.g., polybutylenes,polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes),poly(1-octenes), poly(1-decenes), and mixtures thereof; alkyl-benzenes(e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls,alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes,alkylated diphenyl ethers and alkylated diphenyl sulfides and thederivatives, analogs and homologs thereof or mixtures thereof.

Other synthetic lubricating oils include polyol esters (such asPriolube®3970), diesters, liquid esters of phosphorus-containing acids(e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester ofdecane phosphonic acid), or polymeric tetrahydrofurans. Synthetic oilsmay be produced by Fischer-Tropsch reactions and typically may behydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodimentoils may be prepared by a Fischer-Tropsch gas-to-liquid syntheticprocedure as well as other gas-to-liquid oils.

Oils of lubricating viscosity may also be defined as specified in theAmerican Petroleum Institute (API) Base Oil InterchangeabilityGuidelines. The five base oil groups are as follows: Group I (sulfurcontent >0.03 wt %, and/or <90 wt % saturates, viscosity index 80-120);Group II (sulfur content <0.03 wt %, and >90 wt % saturates, viscosityindex 80-120); Group III (sulfur content <0.03 wt %, and >90 wt %saturates, viscosity index >120); Group IV (all polyalphaolefins(PAOs)); and Group V (all others not included in Groups I, II, III, orIV).

The oil of lubricating viscosity may also be an API Group II+base oil,which term refers to a Group II base oil having a viscosity indexgreater than or equal to 110 and less than 120, as described in SAEpublication “Design Practice: Passenger Car Automatic Transmissions”,fourth Edition, AE-29, 2012, page 12-9, as well as in U.S. Pat. No.8,216,448, column 1 line 57.

The oil of lubricating viscosity may also be an API Group III+base oil,which term refers to a Group III+base oil having a viscosity indexgreater than or equal to 130. Group III+ are known in the art and isdescribed in “Lube Report”, dated Feb. 26, 2014 in an article entitled“SK Sees Group III Shortfall”, by Nancy DeMarco. The article may beobtained fromhttp://www.aselube.com/media/11910/sk_sees_group_iii_shortfall.pdf.

The oil of lubricating viscosity may be an API Group IV oil, or mixturesthereof, i.e., a polyalphaolefin. The polyalphaolefin may be prepared bymetallocene catalyzed processes or from a non-metallocene process.

The oil of lubricating viscosity may comprise an API Group I, or GroupII, or Group III, or Group IV, or Group V oil, or mixtures thereof.

The amount of the oil of lubricating viscosity present may be typicallythe balance remaining after subtracting from 100 wt % the sum of theamount of the additive as described herein above, and the otherperformance additives.

The lubricating composition may be in the form of a concentrate and/or afully formulated lubricant. If the lubricating composition of thedisclosed technology is in the form of a concentrate (which may becombined with additional oil to form, in whole or in part, a finishedlubricant), the ratio of the of components of the disclosed technologyto the oil of lubricating viscosity and/or to diluent oil include theranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.

In one embodiment the lubricating composition may be a non-aqueouscomposition.

The oil of lubricating viscosity may refer to a single base oil or amixture of base oils. The oil of lubricating viscosity used in thelubricating composition of the present invention may have a kinematicviscosity of 2 cSt to 20 cSt (or mm²/s) at 100° C., as measured by ASTMD445-14. The lubricating composition may be liquid, i.e., not a gel orsemi-solid, at ambient temperatures (5-30° C.).

Detergents

The lubricating composition of the present invention contains a metalcontaining sulfur-free detergent and an alkaline earth metal containingsulfonate detergent. In addition, the lubricating composition maycontain small amounts of sulfur-coupled phenate detergents.

As used herein the term “soap” means the surfactant portion of adetergent and does not include a metal base, such as calcium carbonate.The “soap content”, metal ratio and TBN are known to a person skilled inthe art and explained in standard textbook entitled “Chemistry andTechnology of Lubricants”, Third Edition, Edited by R. M. Mortier and S.T. Orszulik, Copyright 2010, pages 219 to 220 under the sub-heading7.2.5. Detergent Classification. The term “soap” may also be referred toas a detergent substrate. For example, the sulfonate detergentsdescribed herein, the soap may be a neutral salt of analkylbenzenesulfonic acid.

In addition, as used herein all total base number values cited aredetermined by ASTM Method D2896-11.

Metal-containing detergents are often referred to as “overbased metaldetergents.” Overbased metal detergents may be viewed as comprising anoil-soluble neutral metal salt component and a metal carbonatecomponent. Overbased materials, otherwise referred to as overbased orsuperbased salts, are generally homogeneous Newtonian systemscharacterized by a metal content in excess of that which would bepresent for neutralization according to the stoichiometry of the metaland the particular acidic organic compound reacted with the metal. Theoverbased materials are prepared by reacting an acidic material(typically an inorganic acid or lower carboxylic acid, in one embodimentcarbon dioxide) with a mixture comprising an acidic organic compound, areaction medium comprising at least one inert, organic solvent (e.g.,mineral oil, naphtha, toluene, xylene) for the acidic organic material,a stoichiometric excess of a metal base, and a promoter such as a phenolor alcohol and optionally ammonia. The acidic organic material willnormally have a sufficient number of carbon atoms, for instance, as ahydrocarbyl substituent, to provide a reasonable degree of solubility inoil. The amount of excess metal is commonly expressed in terms of metalratio. The term “metal ratio” is the ratio of the total equivalents ofthe metal to the equivalents of the acidic organic compound. A neutralmetal salt has a metal ratio of one. A salt having 4.5 times as muchmetal as present in a normal salt will have metal excess of 3.5equivalents, or a ratio of 4.5.

Overbased detergents are often characterized by Total Base Number(TBN—ASTM D2896-11). TBN is the amount of strong acid needed toneutralize all of the overbased material's basicity, expressed aspotassium hydroxide equivalents (mg KOH per gram of sample). Sinceoverbased detergents are commonly provided in a form which contains acertain amount of diluent oil, for example, 40-50% oil, the actual TBNvalue for such a detergent will depend on the amount of such diluent oilpresent, irrespective of the “inherent” basicity of the overbasedmaterial. For the purposes of the present invention, the TBN of anoverbased detergent is to be recalculated to an oil-free basis.Detergents which are useful in the lubricating composition of thepresent invention may have a TBN (oil-free basis) of 100 to 800, and inone embodiment 150 to 750, and in another, 400 to 700. If multipledetergents are employed, the overall TBN of the detergent component(that is, an average of all the specific detergents together) willtypically be in the above ranges.

The metal compounds useful in making the basic metal salts are generallyany Group 1 or Group 2 metal compounds (CAS version of the PeriodicTable of the Elements). The Group 1 metals of the metal compound includeGroup 1a alkali metals such as sodium, potassium, and lithium, as wellas Group 1b metals such as copper. The Group 1 metals can be sodium,potassium, lithium and copper, and in one embodiment sodium orpotassium, and in another embodiment, sodium. The Group 2 metals of themetal base include the Group 2a alkaline earth metals such as magnesium,calcium, and barium, as well as the Group 2b metals such as zinc orcadmium. In one embodiment, the Group 2 metals are magnesium, calcium,barium, or zinc, and in another embodiments magnesium or calcium. Incertain embodiments, the metal is calcium or sodium or a mixture ofcalcium and sodium. Generally the metal compounds are delivered as metalsalts. The anionic portion of the salt can be hydroxide, oxide,carbonate, borate, or nitrate.

The lubricating composition of the present invention comprises anoverbased detergent. In particular, the lubricating composition of thepresent invention comprises one or more detergents derived from analkylphenol. In one embodiment, the metal containing detergent derivedfrom an alkylphenol is sulfur-free.

In one embodiment, the metal-containing detergent derived from analkylphenol may be an overbased phenate detergent. The phenols useful inmaking phenate detergents can be represented by the formula(R¹)_(a)—Ar—(OH)_(b), wherein R¹ is an aliphatic hydrocarbyl group of 4to 400 carbon atoms, or 6 to 80 or 6 to 30 or 8 to 25 or 8 to 15 carbonatoms; Ar is an aromatic group (which can be a benzene group or anotheraromatic group such as naphthalene); a and b are independently numbersof at least one, the sum of a and b being in the range of two up to thenumber of displaceable hydrogens on the aromatic nucleus or nuclei ofAr. In one embodiment, a and b are independently numbers in the range of1 to 4, or 1 to 2. R¹ and a are typically such that there are an averageof at least 8 aliphatic carbon atoms provided by the R¹ groups for eachphenol compound. Phenate detergents are also sometimes provided assulfur-bridged species. The lubricating composition of the presentinvention may comprise at least one sulfur-free phenate detergent. Inanother embodiment, the lubricating composition contains less than 0.2wt %, or even less than 0.15 wt %. of a sulfur-coupled phenatedetergent. In another embodiment, the lubricating composition issubstantially free of sulfur-coupled phenate detergents. In stillanother embodiment, the lubricating composition is free ofsulfur-coupled phenate detergents.

In one embodiment, the overbased alkyl-phenol based detergent may be anoverbased saligenin detergent. Overbased saligenin detergents arecommonly overbased magnesium salts which are based on saligeninderivatives. A general example of such a saligenin derivative can berepresented by Formula (1):

wherein X comprises —CHO or —CH₂OH, Y comprises —CH₂— or —CH₂OCH₂—, andwherein such —CHO groups typically comprise at least 10 mole percent ofthe X and Y groups; M is hydrogen, ammonium, or a valence of a metal ion(that is to say, in the case of a multivalent metal ion, one of thevalences is satisfied by the illustrated structure and other valencesare satisfied by other species such as anions, or by another instance ofthe same structure), R¹ is a hydrocarbyl group containing 1 to 60 carbonatoms, m is 0 to typically 10, and each p is independently 0, 1, 2, or3, provided that at least one aromatic ring contains an R¹ substituentand that the total number of carbon atoms in all R¹ groups is at least7. When m is 1 or greater, one of the X groups can be hydrogen. In oneembodiment, M is a valence of a Mg ion or a mixture of Mg and hydrogen.Saligenin detergents are disclosed in greater detail in U.S. Pat. No.6,310,009, with special reference to their methods of synthesis (Column8 and Example 1) and preferred amounts of the various species of X and Y(Column 6).

In another embodiment, the overbased alkyl-phenol based detergent mayalso comprise salixarate detergents. Salixarate detergents are overbasedmaterials that can be represented by a substantially linear compoundcomprising at least one unit of formula (2) or formula (3):

each end of the compound having a terminal group of formula (4) or (5):

such groups being linked by divalent bridging groups A, which may be thesame or different for each linkage; wherein in formulas (2)-(5) R³ ishydrogen or a hydrocarbyl group or a valence of a metal ion; R² ishydroxyl or a hydrocarbyl group and j is 0, 1, or 2; R⁶ is hydrogen, ahydrocarbyl group, or a hetero-substituted hydrocarbyl group; either R⁴is hydroxyl and R⁵ and R⁷ are independently either hydrogen, ahydrocarbyl group, or hetero-substituted hydrocarbyl group, or else R⁵and R⁷ are both hydroxyl and R⁴ is hydrogen, a hydrocarbyl group, or ahetero-substituted hydrocarbyl group; provided that at least one of R⁴,R⁵, R⁶ and R⁷ is hydrocarbyl containing at least 8 carbon atoms; andwherein the molecules on average contain at least one of unit (2) or (4)and at least one of unit (3) or (5) and the ratio of the total number ofunits (2) and (4) to the total number of units of (3) and (5) in thecomposition is about 0.1:1 to about 2:1. The divalent bridging group“A,” which may be the same or different in each occurrence, includes—CH₂— (methylene bridge) and —CH₂OCH₂— (ether bridge), either of whichmay be derived from formaldehyde or a formaldehyde equivalent (e.g.,paraform, formalin).

Salixarate derivatives and methods of their preparation are described ingreater detail in U.S. Pat. No. 6,200,936 and PCT Publication WO01/56968. It is believed that the salixarate derivatives have apredominantly linear, rather than macrocyclic, structure, although bothstructures are intended to be encompassed by the term “salixarate.”

The alkyl-phenol based overbased detergent used in the lubricatingcomposition of the invention may also be an overbased salicylate whichmay be an alkali metal salt or an alkaline earth metal salt of asubstituted salicylic acid. The salicylic acids may behydrocarbyl-substituted salicylic acids wherein each substituentcontains an average of at least 8 carbon atoms per substituent and 1 to3 substituents per molecule. The substituents can be polyalkenesubstituents, where polyalkenes include homopolymers and interpolymersof polymerizable olefin monomers of 2 to 16, or 2 to 6, or 2 to 4 carbonatoms. The olefins may be monoolefins such as ethylene, propylene,1-butene, isobutene, and 1-octene; or a polyolefinic monomer, such asdiolefinic monomer, such 1,3-butadiene and isoprene. In one embodiment,the hydrocarbyl substituent group or groups on the salicylic acidcontains 7 to 300 carbon atoms and can be an alkyl group having amolecular weight of 150 to 2000. The polyalkenes and polyalkyl groupsare prepared by conventional procedures, and substitution of such groupsonto salicylic acid can be effected by known methods. Alkyl salicylatesmay be prepared from an alkylphenol by Kolbe-Schmitt reaction;alternatively, calcium salicylate can be produced by directneutralization of alkylphenol and subsequent carbonation. Overbasedsalicylate detergents and their methods of preparation are disclosed inU.S. Pat. Nos. 4,719,023 and 3,372,116.

In addition to a metal-containing sulfur-free detergent derived from analkylphenol as described above, the lubricating composition of thepresent invention also comprises an overbased sulfonate detergent. Inone embodiment, the overbased sulfonate detergent comprises analkaline-earth metal containing sulfonate detergent. The sulfonatedetergents of the disclosed technology are known to a person skilled inthe art.

Sulfonate detergents are derived from sulfonic acids. Suitable sulfonicacids include sulfonic and thiosulfonic acids. Sulfonic acids includethe mono- or polynuclear aromatic or cycloaliphatic compounds.Oil-soluble sulfonates can be represented for the most part by one ofthe following formulas: R²-T-(SO₃-)_(a) and R³—(SO₃-)_(b), where T is acyclic nucleus such as typically benzene; R² is an aliphatic group suchas alkyl, alkenyl, alkoxy, or alkoxyalkyl; (R²)-T typically contains atotal of at least 15 carbon atoms; and R³ is an aliphatic hydrocarbylgroup typically containing at least 15 carbon atoms. Examples of R³ arealkyl, alkenyl, alkoxyalkyl, and carboalkoxyalkyl groups. The groups T,R², and R³ can also contain other inorganic or organic substituents. Inthe above formulas, a and b are at least 1. In one embodiment thesulfonate detergent may be a predominantly linear alkylbenzenesulfonatedetergent having a metal ratio of at least 8 as described in paragraphs[0026] to [0037] of US Patent Application 2005065045. In someembodiments the linear alkyl group may be attached to the benzene ringanywhere along the linear chain of the alkyl group, but often in the 2,3 or 4 position of the linear chain, and in some instances predominantlyin the 2 position.

In another embodiment, the lubricating composition comprises a sulfonatedetergent, such as a magnesium, sodium or zinc overbased sulfonate.Typically any additional sulfonate detergent may be a magnesium orsodium sulfonate detergent, with magnesium sulfonate the more typical.

In one embodiment, the lubricating composition comprises a 300 TBN orhigher alkaline earth metal sulfonate detergent having a metal ratio of10 to 40, and a 82 to 100 TBN or lower alkaline earth metal sulfonatedetergent having a metal ratio of 3 to 9.

In one embodiment, the lubricating composition comprises a 300 TBN orhigher alkaline earth metal sulfonate detergent, which comprises amagnesium sulfonate detergent having a metal ratio of 10 to 40, and a 80TBN or lower alkaline earth metal sulfonate detergent, which comprises acalcium sulfonate detergent having a metal ratio of 1 to 5.

In another embodiment, the lubricating composition comprises a 300 TBNor higher alkaline earth metal sulfonate detergent, which comprises amixture of a calcium sulfonate detergent having a metal ratio of 10 to40 and a magnesium sulfonate detergent having a metal ratio of 10 to 40,and a 80 TBN or lower alkaline earth metal sulfonate detergent, whichcomprises a calcium sulfonate detergent having a metal ratio of 1 to 5.

The 300 TBN or higher alkaline earth metal sulfonate detergent and the80 TBN or lower alkaline earth metal sulfonate detergent may be preparedfrom the same or different hydrocarbyl-substituted sulfonic acids.Typically the hydrocarbyl-substituted sulfonic acids arealkyl-substituted sulfonic acids.

The sulfonate may be prepared from a mono- or di-hydrocarbyl-substitutedbenzene (or toluene, naphthalene, indenyl, indanyl, orbicyclopentadienyl) sulfonic acid, wherein the hydrocarbyl group maycontain 6 to 40, or 8 to 35 or 9 to 30 carbon atoms.

The hydrocarbyl group may be derived from polypropylene or a linear orbranched alkyl group containing at least 10 carbon atoms. Examples of asuitable alkyl group include branched and/or linear decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, octadecenyl, nonodecyl, eicosyl, un-eicosyl, do-eicosyl,tri-eicosyl, tetra-eicosyl, penta-eicosyl, hexa-eicosyl or mixturesthereof.

In one embodiment the hydrocarbyl-substituted sulfonic acid may includepolypropene benzenesulfonic acid and C₁₆-C₂₄ alkyl benzenesulfonic acid,or mixtures thereof.

In one embodiment the 300 TBN sulfonate detergent may be a predominantlylinear alkylbenzene sulfonate detergent having a metal ratio of having ametal ratio of 10 to 40 as is described in paragraphs [0026] to [0037]of US Patent Application 2005065045 (and granted as U.S. Pat. No.7,407,919). The predominantly linear alkylbenzene sulfonate detergentmay be particularly useful for assisting in improving fuel economy.

Typically the 300 TBN or higher alkaline earth metal sulfonate detergenthas a metal ratio of 12 to 30, or 12 to 22, or 16 to 20, or 10 to 20, or20 to 30, or 22 to 25. In one embodiment the 300 TBN metal ratio may be16 to 20, and in another embodiment 22 to 25.

In one embodiment the lubricating composition comprises a calciumsulfonate detergent having a metal ratio of 10 to 40, and a calciumsulfonate detergent having a metal ratio of 3 to 9.

In one embodiment the lubricating composition comprises a calciumsulfonate detergent having a metal ratio of 10 to 40, a calciumsulfonate detergent having a metal ratio of 3 to 9, and a magnesiumsulfonate detergent having a metal ratio of 12 to 40.

The magnesium sulfonate detergent may have a TBN of 300 to 800, or 450to 700 mg KOH/g; and a metal ratio of 12 to 40, or 14 to 25. Themagnesium sulfonate may have the same or differenthydrocarbyl-substituted sulfonic acids, and are defined the same asdescribed above for calcium sulfonate detergents.

Other overbased detergents can include overbased detergents having aMannich base structure, as disclosed in U.S. Pat. No. 6,569,818.

Overbased materials are well known to those skilled in the art. Patentsdescribing techniques for making basic salts of sulfonic acids,carboxylic acids, (hydrocarbyl-substituted) phenols, phosphonic acids,and mixtures of any two or more of these include U.S. Pat. Nos.2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186;3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.

The lubricating composition of the present invention comprises one ormore metal-containing sulfur-free detergents derived from alkyl-phenol,as described above, in an amount sufficient to deliver at least 0.2weight percent alkylphenol-containing soap to the composition. In someembodiments, the metal-containing sulfur-free detergent may be selectedfrom phenate detergents, alkylsalicylate detergents, Mg saligenin, or Casalixarate.

The lubricating composition of the present invention also comprises oneor more sulfonate detergents in an amount to deliver at least 0.8 weightpercent sulfonate soap to the composition. In one embodiment, thesulfonate detergent is an alkaline earth metal sulfuonate detergent.

Succinimide Dispersant

The lubricating composition further comprises a succinimide dispersant.In one embodiment, the lubricating composition comprises 1 wt % to 4.5wt % or 1 wt % to 4 wt % polyisobutylene succinimide dispersant.

Succinimide dispersants may be derived from polyisobutylene succinimide,wherein the polyisobutylene from which polyisobutylene succinimide maybe derived has a number average molecular weight of 350 to 5000, or 750to 3000 or 1550 to 2500.

In certain embodiments, the dispersant is prepared by a process thatinvolves the presence of small amounts of chlorine or other halogen, asdescribed in U.S. Pat. No. 7,615,521 (see, e.g., col. 4, lines 18-60 andpreparative example A). Such dispersants typically have some carbocyclicstructures in the attachment of the hydrocarbyl substituent to theacidic or amidic “head” group. In other embodiments, the dispersant isprepared by a thermal process involving an “ene” reaction, without theuse of any chlorine or other halogen, as described in U.S. Pat. No.7,615,521; dispersants made in this manner are often derived from highvinylidene (i.e. greater than 50% terminal vinylidene)polyisobutylene(See col. 4, line 61 to col. 5, line 30 and preparativeexample B). Such dispersants typically do not contain theabove-described carbocyclic structures at the point of attachment. Incertain embodiments, the dispersant is prepared by free radicalcatalyzed polymerization of high-vinylidene polyisobutylene with anethylenically unsaturated acylating agent, as described in U.S. Pat. No.8,067,347.

Dispersants may be derived from, as the polyolefin, high vinylidenepolyisobutylene, that is, having greater than 50, 70, or 75% terminalvinylidene groups (a and β isomers). In certain embodiments, thesuccinimide dispersant may be prepared by the direct alkylation route.In other embodiments it may comprise a mixture of direct alkylation andchlorine-route dispersants.

Suitable dispersants for use in the compositions of the presentinvention include succinimide dispersants. In one embodiment, thedispersant may be present as a single dispersant. In one embodiment, thedispersant may be present as a mixture of two or three differentdispersants, wherein at least one may be a succinimide dispersant.

The dispersant may also be post-treated by conventional methods by areaction with any of a variety of agents. Among these are boroncompounds, urea, thiourea, dimercaptothiadiazoles, carbon disulfide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhydrides, maleic anhydride, nitriles, epoxides, and phosphoruscompounds.

The dispersant of polyisobutylene succinimide may be derived from analiphatic polyamine, or mixtures thereof. In one embodiment, thelubricating composition comprises a non-borated succinimide dispersant.

The aliphatic polyamine may be aliphatic polyamine such as anethylenepolyamine, a propylenepolyamine, a butylenepolyamine, ormixtures thereof. In one embodiment the aliphatic polyamine may beethylenepolyamine. In one embodiment the aliphatic polyamine may bechosen from ethylenediamine, diethylenetriamine, triethylenetetramine,tetraethylene-pentamine, pentaethylenehexamine, polyamine still bottoms,and mixtures thereof.

Polyisobutylene succinimide dispersants and their preparation aredisclosed, for instance in U.S. Pat. Nos. 3,172,892, 3,219,666,3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170,3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re26,433, and 6,165,235, 7,238,650 and EP Patent Application 0 355 895 A.

The polyisobutylene succinimide may have a carbonyl to nitrogen ratio of1:1 to 1:5, or 1:1 to 1:4, or 1:1.3 to 3: or 1:1.5 to 1:2, or 1:1.4 to1:0.6.

In one embodiment the polyisobutylene succinimide dispersant may includean amine-functionalized additive may be derived from an amine having atleast 3 or 4 aromatic groups.

As used herein the term “an aromatic group” is used in the ordinarysense of the term and is known to be defined by Hückel theory of 4n+2 πelectrons per ring system. Accordingly, one aromatic group may have 6,or 10, or 14 π electrons. Hence a benzene ring has 6 π electrons, anaphthylene ring has 10 π electrons and an acridine group has 14 πelectrons. An example of the amine having at least 3 or 4 aromaticgroups may be represented by Formula (6):

wherein independently each variable,R¹ may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);R² may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);U may be an aliphatic, alicyclic or aromatic group, with the provisothat when U may be aliphatic, the aliphatic group may be linear orbranched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; andw may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

An example of the amine having at least 3 or 4 aromatic groups may berepresented by Formula (6a):

wherein independently each variable,R¹ may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);R² may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);U may be an aliphatic, alicyclic or aromatic group, with the provisothat when U may be aliphatic, the aliphatic group may be linear orbranched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; andw may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

Alternatively, the compound of Formula (6a) may also be represented by:

wherein each variable U, R¹, and R² are the same as described above andw may be 0 to 9 or 0 to 3 or 0 to 1 (typically 0).

Examples of an amine having at least 3 or 4 aromatic groups may berepresented by any of the following Formulae (7) and/or (8):

In one embodiment the amine having at least 3 or 4 aromatic groups mayinclude mixtures of compounds represented by the formulae disclosedabove. A person skilled in the art will appreciate that compounds ofFormulae (7) and (8) may also react with the aldehyde described below toform acridine derivatives. Acridine derivatives that may be formedinclude compounds illustrated represented by Formula (7a) or (8a) to(8c) below. In addition to these compounds represented these formulae, aperson skilled in the art will also appreciate that other acridinestructures may be possible where the aldehyde reacts with other withbenzyl groups bridged with the >NH group. Examples of acridinestructures include those represented by Formulae (7a), (8a) or (8b) or(8c):

Any or all of the N-bridged aromatic rings are capable of such furthercondensation and perhaps aromaticisation. One other of many possiblestructures include Formula (8b):

Any of the formulae above (7), (7a) (8), or (8a) to (8c) could also havefurther condensation reactions occurring resulting in one or moreacridine moieties forming per molecule.

Examples of the amine having at least 3 or 4 aromatic groups may bebis[p-(p-aminoanilino)phenyl]-methane,2-(7-amino-acridin-2-ylmethyl)-N-4-{4-[4-(4-amino-phenylamino)-benzyl]-phenyl}-benzene-1,4-diamine,N-4-[4-{4-(4-amino-phenylamino)-benzyl]-phenyl}-2-[4-(4-amino-phenylamino)-cyclohexa-1,5-dienylmethyl]benzene-1,4-diamine,N-[4-(7-amino-acridin-2-ylmethyl)-phenyl]benzene-1,4-diamine, ormixtures thereof.

In one embodiment the amine having at least 3 or 4 aromatic groups maybe bis[p-(p-aminoanilino)phenyl]-methane,2-(7-amino-acridin-2-ylmethyl)-N-4-{4-[4-(4-amino-phenylamino)-benzyl]-phenyl}-benzene-1,4-diamine or mixtures thereof.

The amine having at least 3 or 4 aromatic groups may be prepared by aprocess comprising reacting an aldehyde with an amine (typically 4aminodiphenylamine). The resultant amine may be described as an alkylenecoupled amine having at least 3 or 4 aromatic groups, at least one —NH₂functional group, and at least 2 secondary or tertiary amino groups.

The aldehyde may be aliphatic, alicyclic or aromatic. The aliphaticaldehyde may be linear or branched. Examples of a suitable aromaticaldehyde include benzaldehyde or o-vanillin. Examples of an aliphaticaldehyde include formaldehyde (or a reactive equivalent thereof such asformalin or paraformaldehyde), ethanal or propanal. Typically thealdehyde may be formaldehyde or benzaldehyde.

Alternatively, the amine having at least 3 or 4 aromatic groups may alsobe prepared by the methodology described in Berichte der DeutschenChemischen Gesellschaft (1910), 43, 728-39.

In one embodiment the amine having at least 3 or 4 aromatic groups maybe obtained/obtainable by a process comprising reacting isatoicanhydride or alkyl substituted isatoic anhydride, with an aromatic aminewith at least two aromatic groups and a reactive primary or secondaryamino group. The resultant material may be described as an anthranilicderivative.

In one embodiment the anthranilic derivative may be prepared in areaction containing isatoic anhydride or alkyl substituted isatoicanhydride and an aromatic amine selected from the group consisting ofxylylenediamine, 4-aminodiphenylamine, 1,4-dimethylphenylenediamine, andmixtures thereof. In one embodiment the aromatic amine may be4-aminodiphenylamine.

The process described above to prepare the anthranilic derivative may becarried out at a reaction temperature in the range of 20° C. to 180° C.,or 40° C. to 110° C. The process may or may not be carried out in thepresence of a solvent. Examples of a suitable solvent include water,diluent oil, benzene, t-butyl benzene, toluene, xylene, chlorobenzene,hexane, tetrahydrofuran, or mixtures thereof. The reactions may beperformed in either air or an inert atmosphere. Examples of suitableinert atmosphere include nitrogen or argon, typically nitrogen.

Dispersant Viscosity Modifier

The lubricating composition of the present invention also comprises adispersant viscosity modifier. The lubricating composition comprises 0.1to 1.2 wt % dispersant viscosity modifier. In one embodiment, thelubricating composition comprises 0.1 to 1.2 wt % of a dispersantviscosity modifier as described herein that has a number averagemolecular weight of at least 20,000.

The dispersant viscosity modifier may include functionalizedpolyolefins, for example, ethylene-propylene copolymers that have beenfunctionalized with an acylating agent such as maleic anhydride and anamine; polymethacrylates functionalized with an amine, or styrene-maleicanhydride copolymers reacted with an amine. More detailed description ofdispersant viscosity modifiers are disclosed in InternationalPublication WO2006/015130 or U.S. Pat. Nos. 4,863,623; 6,107,257;6,107,258; 6,117,825; and 7,790,661. In one embodiment the dispersantviscosity modifier may include those described in U.S. Pat. No.4,863,623 (see column 2, line 15 to column 3, line 52) or inInternational Publication WO2006/015130 (see page 2, paragraph [0008]and preparative examples are described paragraphs [0065] to [0073]).

In one particular embodiment the dispersant viscosity modifier comprisesan olefin copolymer further functionalized with a dispersant aminegroup. Typically, the olefin copolymer may be an ethylene-propylenecopolymer.

The dispersant amine group may be prepared/derived from reacting theolefin copolymer (typically, an ethylene-propylene copolymer) with anacylating agent (typically maleic anhydride) and an aromatic aminehaving a primary or secondary amino group. Typically, the dispersantviscosity modifier may be an ethylene-propylene copolymer acylated withmaleic anhydride and reacted with an aromatic amine.

The formation of a dispersant viscosity modifier is well known in theart. The dispersant viscosity modifier may include for instance thosedescribed in U.S. Pat. No. 7,790,661 column 2, line 48 to column 10,line 38.

In one embodiment the dispersant viscosity modifier may be prepared bygrafting of an olefinic carboxylic acid acylating agent onto a polymerof 15 to 80 mole percent of ethylene, from 20 to 85 mole percent ofC₃₋₁₀ α-monoolefin, and from 0 to 15 mole percent of non-conjugateddiene or triene, said polymer having an average molecular weight rangingfrom 5000 to 500,000, and further reacting said grafted polymer with anamine (typically an aromatic amine).

In another embodiment the dispersant viscosity modifier may be areaction product of: (a) a polymer comprising carboxylic acidfunctionality or a reactive equivalent thereof, said polymer having anumber average molecular weight of greater than 5,000; and (b) an aminecomponent comprising at least one aromatic amine containing at least oneamino group capable of condensing with said carboxylic acidfunctionality to provide a pendant group and at least one additionalgroup comprising at least one nitrogen, oxygen, or sulfur atom, whereinsaid aromatic amine may be chosen from (i) a nitro-substituted aniline,(ii) an amine comprising two aromatic moieties linked by a —C(O)NR—group, a —C(O)O— group, an —O— group, an —N═N— group, or an —SO₂— groupwhere R may be hydrogen or hydrocarbyl, one of said aromatic moietiesbearing said condensable amino group, (iii) an aminoquinoline, (iv) anaminobenzimidazole, (v) an N,N-dialkylphenylenediamine, (vi), anaminodiphenylamine (also N,N-phenyldiamine), and (vii) aring-substituted benzylamine.

The aromatic amine of the dispersant viscosity modifier may also includethose which can be represented by the general structure NH₂—Ar orT-NH—Ar, where T may be alkyl or aromatic, Ar may be an aromatic group,including nitrogen-containing or amino-substituted aromatic groups andAr groups including any of the following structures

as well as multiple non-condensed or linked aromatic rings. In these andrelated structures, R^(v), R^(vi), and R^(vii) can be independently,among other groups disclosed herein, —H, —C₁₋₁₈ alkyl groups, nitrogroups, —NH—Ar, —N═N—Ar, —NH—CO—Ar, —OOC—Ar, —OOC—C₁₋₁₈ alkyl,—COO—C₁₋₁₈ alkyl, —OH, —O—(CH₂CH₂—O)_(n)C₁₋₁₈ alkyl groups, and—O—(CH₂CH₂O)_(n)Ar (where n may be 0 to 10).

Aromatic amines include those amines wherein a carbon atom of thearomatic ring structure is attached directly to the amino nitrogen. Theamines may be monoamines or polyamines. The aromatic ring will typicallybe a mononuclear aromatic ring (i.e., one derived from benzene) but caninclude fused aromatic rings, especially those derived from naphthalene.Examples of aromatic amines include aniline, N-alkylanilines such asN-methylaniline and N-butylaniline, di-(para-methylphenyl)amine,4-aminodiphenylamine, N,N-dimethylphenylenediamine, naphthylamine,4-(4-nitrophenylazo)aniline (disperse orange 3), sulphamethazine,4-phenoxyaniline, 3-nitroaniline, 4-aminoacetanilide(N-(4-aminophenyl)acetamide)), 4-amino-2-hydroxy-benzoic acid phenylester (phenyl amino salicylate), N-(4-amino-phenyl)-benzamide, variousbenzyl amines such as 2,5-dimethoxybenzylamine, 4-phenylazoaniline, andsubstituted versions of these. Other examples includepara-ethoxyaniline, para-dodecyl aniline, cyclohexyl-substitutednaphthylamine, and thienyl-substituted aniline. Examples of othersuitable aromatic amines include amino-substituted aromatic compoundsand amines in which the amine nitrogen is a part of an aromatic ring,such as 3-aminoquinoline, 5-aminoquinoline, and 8-aminoquinoline. Alsoincluded are aromatic amines such as 2-aminobenzimidazole, whichcontains one secondary amino group attached directly to the aromaticring and a primary amino group attached to the imidazole ring. Otheramines include N-(4-anilinophenyl)-3-aminobutanamide or 3-amino propylimidazole. Yet other amines include 2,5-dimethoxybenzylamine.

Additional aromatic amines and related compounds are disclosed in U.S.Pat. Nos. 6,107,257 and 6,107,258; some of these includeaminocarbazoles, benzoimidazoles, aminoindoles, aminopyrroles,amino-indazolinones, aminoperimidines, mercaptotriazoles,aminophenothiazines, aminopyridines, aminopyrazines, aminopyrimidines,pyridines, pyrazines, pyrimidines, aminothiadiazoles,aminothiothiadiazoles, and aminobenzotriaozles. Other suitable aminesinclude 3-amino-N-(4-anilinophenyl)-N-isopropyl butanamide, andN-(4-anilinophenyl)-3-{(3-aminopropyl)-(cocoalkyl)amino} butanamide.Other aromatic amines which can be used include various aromatic aminedye intermediates containing multiple aromatic rings linked by, forexample, amide structures. Examples include materials of the generalstructure:

and isomeric variations thereof, where R^(viii) and R^(ix) areindependently alkyl or alkoxy groups such as methyl, methoxy, or ethoxy.In one instance, R^(viii) and R^(ix) are both —OCH₃ and the material isknown as Fast Blue RR [CAS#6268-05-9].

In another instance, R^(ix) may be —OCH₃ and R^(viii) may be —CH₃, andthe material is known as Fast Violet B [99-21-8]. When both R^(viii) andR^(ix) are ethoxy, the material is Fast Blue BB [120-00-3]. U.S. Pat.No. 5,744,429 discloses other aromatic amine compounds, particularlyaminoalkylphenothiazines. N-aromatic substituted acid amide compounds,such as those disclosed in U.S. Patent Application 2003/0030033 A1, mayalso be used for the purposes of the disclosed technology. Suitablearomatic amines include those in which the amine nitrogen is asubstituent on an aromatic carboxyclic compound, that is, the nitrogenis not sp² hybridized within an aromatic ring.

The aromatic amine may also comprise an amine formed by reacting analdehyde with 4-aminodiphenylamine. The resultant amine may be describedas an alkylene coupled amine having at least 4 aromatic groups, at leastone —NH₂ functional group, and at least 2 secondary or tertiary aminogroups. The aldehyde may be aliphatic, alicyclic or aromatic. Thealiphatic aldehyde may be linear or branched. Examples of a suitablearomatic aldehyde include benzaldehyde or o-vanillin. Examples of analiphatic aldehyde include formaldehyde (or a reactive equivalentthereof such as formalin or paraformaldehyde), ethanal or propanal.Typically the aldehyde may be formaldehyde or benzaldehyde.Alternatively, this aromatic amine may also be prepared by themethodology described in Berichte der Deutschen Chemischen Gesellschaft(1910), 43, 728-39.

The aromatic amine formed by coupling an aldehyde and4-aminodiphenylamine is described European Patent application EP 2 401348 A in and may also be represented by the formula:

wherein each variableR¹ may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);R² may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);U may be an aliphatic, alicyclic or aromatic group, with the provisothat when U may be aliphatic, the aliphatic group may be linear orbranched alkylene group containing 1 to 5, or 1 to 2 carbon atoms; andw may be 0 to 9 or 0 to 3 or 0 to 1 (typically 0).

In one embodiment the aromatic amine includes 4-aminodiphenylamine,aldehyde (typically formaldehyde) coupled 4-aminodiphenylamine,nitro-aniline (3-nitro-aniline), disperse orange-3 (D03), or mixturesthereof.

The lubricating composition of the present invention comprises adispersant viscosity modifier derived from a polyolefin having a numberaverage molecular weight of at least 20,000. In one embodiment, thelubricating composition may contain a mixture of low molecular weightand high molecular weight dispersant viscosity modifiers, provided thatthe overall number average molecular weight of the dispersant viscositymodifier is at least 20,000. As used herein, low molecular weightdispersant viscosity modifiers are derived from polyolefin copolymershaving a number average molecular weight below 20,000, or even 10,000 orlower. High molecular weight dispersant viscosity modifiers are derivedfrom polyolefin copolymers having a number average molecular weight ofgreater than 20,000, or even 40,000 or greater, or even 45,000 orgreater, such as 40,000 to 1,000,000. For instance, in one embodiment,the lubricating composition of the present invention may comprise adispersant viscosity modifier wherein the dispersant viscosity modifiercomprises a mixture of at least one low molecular weight dispersantviscosity modifier derived from a polyolefin having a number averagemolecular weight of less than 20,000, and at least one high molecularweight dispersant viscosity modifier derived from a polyolefin having anumber average molecular weight of at least 40,000. For example, in theaforementioned embodiment, the low molecular weight dispersant viscositymodifier may be derived from a polyolefin having a number averagemolecular weight of 10,000. Further for example, in the aforementionedembodiment, the high molecular weight dispersant viscosity modifier maybe derived from a polyolefin having a number average molecular weight of45,000 or greater.

Other Performance Additives

The lubricating composition of the disclosed technology optionallycomprises other performance additives. The other performance additivesinclude at least one of antioxidants, metal deactivators, viscositymodifiers, friction modifiers, antiwear agents, corrosion inhibitors,extreme pressure agents, foam inhibitors, demulsifiers, pour pointdepressants, seal swelling agents and mixtures thereof. Typically,fully-formulated lubricating oil will contain one or more of theseperformance additives.

The lubricating composition optionally further includes at least oneantiwear agent.

Examples of suitable antiwear agents include titanium compounds, esters,amides, and/or imides of alpha-hydroxycarboxylic acids (such as tartaricacid, malic acid, citric acid, glycolic acid), oil soluble amine saltsof phosphorus compounds, sulfurized olefins, metaldihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates),phosphites (such as dibutyl phosphite), phosphonates,thiocarbamate-containing compounds, such as thiocarbamate esters,thiocarbamate amides, thiocarbamic ethers, alkylene-coupledthio-carbamates, and bis(S-alkyldithiocarbamyl) disulfides. The antiwearagent may in one embodiment include a tartrate, or tartrimide asdisclosed in International Publication WO 2006/044411 or Canadian PatentCA 1 183 125. The tartrate or tartrimide may contain alkyl-ester groups,where the sum of carbon atoms on the alkyl groups may be at least 8. Theantiwear agent may in one embodiment include a citrate as is disclosedin US Patent Application 20050198894.

Another class of additives includes oil-soluble titanium compounds asdisclosed in U.S. Pat. No. 7,727,943 and US2006/0014651. The oil-solubletitanium compounds may function as antiwear agents, friction modifiers,antioxidants, deposit control additives, or more than one of thesefunctions. In one embodiment the oil soluble titanium compound may be atitanium (IV) alkoxide. The titanium alkoxide may be formed from amonohydric alcohol, a polyol or mixtures thereof. The monohydricalkoxides may have 2 to 16, or 3 to 10 carbon atoms. In one embodiment,the titanium alkoxide may be titanium (IV) isopropoxide. In oneembodiment, the titanium alkoxide may be titanium (IV) 2-ethylhexoxide.In one embodiment, the titanium compound comprises the alkoxide of avicinal 1,2-diol or polyol. In one embodiment, the 1,2-vicinal diolcomprises a fatty acid mono-ester of glycerol, often the fatty acid maybe oleic acid.

In one embodiment, the oil soluble titanium compound may be a titaniumcarboxylate. In a further embodiment the titanium (IV) carboxylate maybe titanium neodecanoate.

The lubricating composition may in one embodiment further include aphosphorus-containing antiwear agent. Typically thephosphorus-containing antiwear agent may be a zincdialkyldithiophosphate, phosphite, phosphate, phosphonate, and ammoniumphosphate salts, or mixtures thereof. Zinc dialkyldithiophosphates areknown in the art.

In one embodiment the lubricating composition may further include aphosphorus-containing antiwear agent based upon zincdialkyldithiophosphate, or mixtures thereof.

The zinc dialkyldithiophosphate may be derived from aliphatic oraromatic hydrocarbyl alcohols; the hydrocarbyl; alcohols may be primaryor secondary alcohols. A zinc dialkyldithiophosphate (or ZDDP) derivedfrom secondary alcohols is said to be a secondary ZDDP. A ZDDP derivedfrom primary alcohols is said to be a primary ZDDP. ZDDP prepared from amixture of primary and secondary alcohols is said to be a mixedprimary/secondary ZDDP. In one embodiment the ZDDP may be represented bythe following structure:

wherein each R may be independently a primary or secondary hydrocarbylgroup containing from 1 to 24, for example from 2 to 12 carbon atoms andincluding groups such as alkyl, alkenyl, aryl, arylalkyl, alkaryl andcycloaliphatic hydrocarbyl groups. In an embodiment, R may be alkylgroups of 2 to 8 carbon atoms. In another embodiment, R may be an alkylgroup having 5 or more carbon atoms. R may be, for example, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl,n-octyl, decyl, dodecyl, octadecyl, 2-ethylehexyl, phenyl, butylphenyl,cyclohexyl, methylcyclopentyl, propenyl, and butenyl.

The R group of the zinc dithiophosphate may be derived, for example,from a primary alcohol such as methanol, ethanol, propanol, butanol,pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol,octadecanol, propenol, butenol, 2-ethylhexanol: a secondary alcohol suchas isopropyl alcohol, secondary butyl alcohol, isobutanol,3-methylbutan-2-ol, 2-pentanol, 4-methyl-2-pentanol, 2-hexanol,3-hexanol, amyl alcohol, an aryl alcohol such as phenol, substitutedphenol (particularly alkylphenol such as butylphenol, octylphenol,nonylphenol, dodecylphenol), disubstituted phenol. Certain primary diolsmay also be used to prepare ZDDP; suitable primary diols includeethylene glycol, propylene gycol, and esters of polyhydric alcohol suchas glycerol monooleate and combinations thereof. ZDDP may be preparedfrom a combination of primary alcohols and primary diols.

In one embodiment the R group of the ZDDP may be independently a primaryalkyl, a secondary alkyl, an aryl group, or mixtures thereof.

In one embodiment the R group of the ZDDP may be a secondary alkylgroup.

When present, the amount of metal dialkyldithiophosphate, such as zincdialkyldithiophosphate, is present in amounts sufficient to deliver 0.1wt % or less phosphorous to the lubricating composition. In oneembodiment, the lubricating composition comprises less than 0.1 wt %phosphorous. In another embodiment, the lubricating compositioncomprises 0.08 wt % or less phosphorous, for example 0.01 wt %, to 0.08wt %. In another embodiment, the lubricating composition of the presentinvention comprises a metal dialkyldithiophosphate such as ZDDP, whereinthe alkyl groups in the metal dalkyldithiophosphate have 5 or morecarbon atoms. In another embodiment, the lubricating composition of thepresent invention comprises a metal dialkyldithiophosphate wherein atleast about 65 mol % or even 75 mol % of the alkyl groups have 5 or morecarbon atoms.

In one embodiment, the lubricating composition of the inventioncomprises a metal dialkyldithiophosphate wherein at least about 65 mol %or even 75 mol % of the alkyl groups have 5 or more carbon atoms, suchas 5 to 24 carbon atoms, or even 5 to 12 carbon atoms, or even 6 to 12carbon atoms, and wherein the lubricating composition comprises 1 wt %to 4 wt % of a polyisobutenyl succinimide dispersant.

In one embodiment the friction modifier may be chosen from long chainfatty acid derivatives of amines, long chain fatty esters, orderivatives of long chain fatty epoxides; fatty imidazolines; aminesalts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyltartrimides; fatty alkyl tartramides; fatty glycolates; and fattyglycolamides. The friction modifier may be present at 0 wt % to 6 wt %,or 0.01 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.1 wt % to 2 wt % ofthe lubricating composition.

As used herein the term “fatty alkyl” or “fatty” in relation to frictionmodifiers means a carbon chain having 10 to 22 carbon atoms, typically astraight carbon chain.

Examples of suitable friction modifiers include long chain fatty acidderivatives of amines, fatty esters, or fatty epoxides; fattyimidazolines such as condensation products of carboxylic acids andpolyalkylene-polyamines; amine salts of alkylphosphoric acids; fattyalkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fattyphosphonates; fatty phosphites; borated phospholipids, borated fattyepoxides; glycerol esters; borated glycerol esters; fatty amines;alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl andpolyhydroxy fatty amines including tertiary hydroxy fatty amines;hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkylsalicylates; fatty oxazolines; fatty ethoxylated alcohols; condensationproducts of carboxylic acids and polyalkylene polyamines; or reactionproducts from fatty carboxylic acids with guanidine, aminoguanidine,urea, or thiourea and salts thereof.

Friction modifiers may also encompass materials such as sulfurized fattycompounds and olefins, molybdenum dialkyldithiophosphates, molybdenumdithiocarbamates, sunflower oil or soybean oil monoester of a polyol andan aliphatic carboxylic acid.

In another embodiment the friction modifier may be a long chain fattyacid ester. In another embodiment the long chain fatty acid ester may bea mono-ester and in another embodiment the long chain fatty acid estermay be a triglyceride.

Extreme Pressure (EP) agents include compounds that are soluble in theoil include sulfur- and chlorosulfur-containing EP agents,dimercaptothiadiazole or CS₂ derivatives of dispersants (typicallysuccinimide dispersants), derivative of chlorinated hydrocarbon EPagents and phosphorus EP agents. Examples of such EP agents includechlorinated wax; sulfurized olefins (such as sulfurized isobutylene), ahydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, or oligomersthereof, organic sulfides and polysulfides such as dibenzyl-disulfide,bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methylester of oleic acid, sulfurized alkylphenol, sulfurized dipentene,sulfurized terpene, and sulfurized Diels-Alder adducts;phosphosulfurized hydrocarbons such as the reaction product ofphosphorus sulfide with turpentine or methyl oleate; phosphorus esterssuch as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutylphosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenylphosphite; dipentylphenyl phosphite, tridecyl phosphite, distearylphosphite and polypropylene substituted phenol phosphite; metalthiocarbamates such as zinc dioctyldithiocarbamate and bariumheptylphenol diacid; amine salts of alkyl and dialkylphosphoric acids orderivatives including, for example, the amine salt of a reaction productof a dialkyldithiophosphoric acid with propylene oxide and subsequentlyfollowed by a further reaction with P₂O₅; and mixtures thereof (asdescribed in U.S. Pat. No. 3,197,405).

Foam inhibitors that may be useful in the compositions of the disclosedtechnology include polysiloxanes, copolymers of ethyl acrylate and2-ethylhexylacrylate and optionally vinyl acetate; demulsifiersincluding fluorinated polysiloxanes, trialkyl phosphates, polyethyleneglycols, polyethylene oxides, polypropylene oxides and (ethyleneoxide-propylene oxide) polymers.

Pour point depressants that may be useful in the compositions of thedisclosed technology include polyalphaolefins, esters of maleicanhydride-styrene copolymers, poly(meth)acrylates, polyacrylates orpolyacrylamides.

Demulsifiers include trialkyl phosphates, and various polymers andcopolymers of ethylene glycol, ethylene oxide, propylene oxide, ormixtures thereof.

Metal deactivators include derivatives of benzotriazoles (typicallytolyltriazole), 1,2,4-triazoles, benzimidazoles,2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles. The metaldeactivators may also be described as corrosion inhibitors.

Seal swell agents include sulpholene derivatives Exxon Necton-37™ (FN1380) and Exxon Mineral Seal Oil™ (FN 3200).

INDUSTRIAL APPLICATION

The lubricating composition of the present invention may be used for thelubrication of any of a variety of mechanical equipment types,including, but not limited to, an internal combustion engine, bysupplying thereto the lubricating composition as described herein. Incertain embodiments, the engine may be a diesel (compression ignited)engine, such as a heavy duty diesel engine. Other possible enginesinclude gasoline (spark-ignited) engines, and engines consumingalcohols, gasoline-alcohol mixtures, biodiesel fuels, various mixedfuels, synthetic fuels, or gaseous fuels such as natural gas orhydrogen, two-stroke cycle engines, and marine diesel engines.

The internal combustion engine disclosed herein may have a steel surfaceon a cylinder bore, cylinder block, or piston ring.

The internal combustion engine may have a surface of steel, or analuminium alloy, or an aluminium composite.

Typically the compression-ignition internal combustion engine has amaximum laden mass over 3,500 kg.

The compression-ignition internal combustion engine may be referred toas a heavy duty diesel engine. The laden mass (sometimes referred to asgross vehicle weight rating (GVWR)) may be over 2,700 kg (or 6,000 USApounds) 2,900 kg, or over 3.00 kg, or over 3,300 kg, or over 3,500 kg,or over 3,700 kg, or over 3,900 kg (or 8,500 USA pounds). Typically theupper limit on the laden mass or GVWR may be set by national governmentand may be 10,000 kg, or 9,000 kg, or 8,000 kg, or 7,500 kg. The upperranges of laden mass may be up to 400,000 kg, or up to 200,000 kg, or upto 60,000 kg, or up to 44,000 kg, or up to 40,000 kg. Typically a ladenmass above 120,000 may be for an off-highway vehicle.

Heavy duty diesel engines are noted to be limited to all motor vehicleswith a “technically permissible maximum laden mass” over 3,500 kg,equipped with compression ignition engines or positive ignition naturalgas (NG) or LPG engines. In contrast, the European Union indicates thatfor new light duty vehicles (passenger cars and light commercialvehicles) included within the scope of ACEA testing section “C” have a“technically permissible maximum laden mass” not exceeding 2610 kg.

There is a distinct difference between passenger car, and heavy dutydiesel engines. The difference in size from over 3,500 kg to not morethan 2610 kg means that engines of both types will experiencesignificantly different operating conditions such as load, oiltemperatures, duty cycle and engine speeds. Heavy duty diesel enginesare designed to maximize torque for hauling payloads at maximum fueleconomy while passenger car diesels are designed for commuting peopleand acceleration at maximum fuel economy. The designed purpose of theengine hauling versus communing results in different hardware designsand resulting stresses imparted to lubricant designed to protect andlubricate the engine. Another distinct design difference is theoperating revolution per minute (RPM) that each engine operates at tohaul versus commute. A heavy duty diesel engine such as a typical 12-13litre truck engine would typically not exceed 2200 rpm while a passengercar engine can go up to 4500 rpm.

In one embodiment the internal combustion engine may be a heavy dutydiesel compression ignited (or spark assisted compression ignited)internal combustion engine.

The lubricating composition of the present invention is formulatedcontaining the components and combinations of components as describedherein. The lubricating composition is formulated as a high-temperaturehigh shear fluid having a dynamic viscosity of less than 3.5 cP, or evenless than 3.1 cP, or even less than 3.05 cP as measured according toASTM D4683 at 150° C. In addition, the lubricating composition isformulated to have a kinematic viscosity at 100° C. of 10 cSt or loweras measured according to ASTM D445-17.

The following examples provide illustrations of the invention. Theseexamples are non-exhaustive and are not intended to limit the scope ofthe invention.

Examples

A series of 10W-30 engine lubricants were prepared containing theadditives described above as well as other conventional additives knownto those of ordinary skill in the art. The amounts (wt %) of eachadditive are shown on table 1 below with the balance of the lubricatingcomposition being the base oil. The lubricating compositions wereevaluated for their ability to protect against adhesive wear using ASTMWK53775. The lubricating compositions and test results are summarized inTable 1.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 10W-30 10W-3010W-30 10W-30 10W-30 Group II Base Oil x x x x x Group III Base Oil xGTL Base Oil x x HV-dispersant 0.7 Other succinimide 3.6 4.4 3.7 3.7 3.4dispersant ZDDP 1 (C3/C6) 0.68 1.0 1.0 1.0 0.18 ZDDP 2 (C6 2°) 0.6 HighTBN Ca Sulfonate 0.12 0.54 0.52 0.64 0.22 Low TBN Ca Sulfonate 0.67 0.360.50 0.58 0.87 High TBN Mg Sulfonate 0.38 0.38 S-coupled Phenate 0.50.84 0.29 Methylene coupled phenate 0.37 0.25 0.37 1 (Mg saligenin)Methylene coupled phenate 0.45 2 (Ca salixarate) Ashless Antioxidant 2.51.37 2.7 2.3 2.75 (combo of aminic and phenolic) Low Mn DVM 0.33 0.670.33 0.26 0.33 High Mn DVM-VI 0.26 0.20 0.11 0.26 Improver OCP VIImprover 0.05 0.5 0.46 0.04 Phosphorus (ppm) 759 1119 1100 1099 761 %Calcium 1520 2390 2295 1870 1290 % Magnesium 720 0 3 75 720 KV100 (cSt)10.0 11.9 11.6 9.5 9.9 ASTM D445-17 HTHS (cP) 3.08 3.63 3.46 3.03 3.03(150° C.) ASTM D4683 Total Dispersant 3.6 4.4 3.7 4.4 3.4 Sulfonate Soap0.8 0.6 0.7 0.8 1.0 S-coupled Phenol Soap 0.3 0.6 0.16 0 0 S-free PhenolSoap 0.35 0.00 0.41 0.24 0.35 Total Soap 1.42 1.20 1.26 1.04 1.35 Hoursto Iron Spike 104 156 160 200 200 ASTM WK53775

A series of 5W-30 engine lubricants were prepared containing theadditives described above as well as other conventional additives knownto those of ordinary skill in the art. The amounts (wt %) of eachadditive are shown on table 1 below with the balance of the lubricatingcomposition being the base oil. The lubricating compositions wereevaluated for their ability to protect against adhesive wear using ASTMWK53775. The lubricating compositions and test results are summarized inTable 2.

TABLE 2 Example Example Example Example Example Example 6 7 8 9 10 115W-30 5W-30 5W-30 5W-30 5W-30 5W-30 Group III Base Oil x x GTL Base Oilx x x x PAO x HV-dispersant 1.4 1.4 1.4 1.4 1.4 Other succinimidedispersant 3.7 3.7 3.7 3.7 3.7 3.4 ZDDP 1 (C3/C6) 0.68 0.18 0.68 0.680.18 0.18 ZDDP 2 (C6) 0.6 0.6 0.6 High TBN Ca Sulfonate 0.52 0.52 0.520.52 0.20 0.22 Low TBN Ca Sulfonate 0.50 0.55 0.50 0.50 0.55 0.87 HighTBN Mg Sulfonate 0.42 0.38 S-coupled Phenate 0.29 0.29 0.29 0.29Methylene coupled phenate 1 0.25 0.37 (Mg saligenin) Methylene coupledphenate 2 0.45 0.45 0.45 0.45 (Ca salixarate) Ashless Antioxidant (comboof 2.6 2.6 2.6 2.6 2.8 2.85 aminic and phenolic) Low Mn DVM 0.33 0.330.33 0.33 0.26 0.33 High Mn DVM-VI Improver 0.26 0.26 0.26 0.26 0.240.26 Styrene-diene VM 0.3 0.4 Phosphorus (ppm) 770 763 770 770 761 761 %Calcium 2295 2295 2295 2295 950 1290 % Magnesium 3 3 3 3 750 720 KV1009.7 9.7 9.7 10.5 9.9 10.0 HTHS (150 C) 3.04 3.09 3.04 3.17 3.02 3.00ASTM D4683 Total Dispersant 5.1 5.1 5.1 5.1 5.1 3.4 Sulfonate Soap 0.70.7 0.7 0.7 0.7 1.0 S-coupled Phenol Soap 0.16 0.16 0.16 0.16 0 0 S-freePhenol Soap 0.41 0.41 0.41 0.41 0.24 0.35 Total Soap 1.26 1.26 1.26 1.260.98 1.35 Hours to Iron Spike 34 60 64 99.5 140 200 ASTM WK53775

The formulations of Examples 4, 5, and 11 in particular showsurprisingly improved performance in protecting against adhesive wear.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. The productsformed thereby, including the products formed upon employing lubricantcomposition of the disclosed technology in its intended use, may not besusceptible of easy description. Nevertheless, all such modificationsand reaction products are included within the scope of the disclosedtechnology; the disclosed technology encompasses lubricant compositionprepared by admixing the components described above.

As used herein reference to the amounts of additives present in thelubricating composition disclosed herein are quoted on an oil freebasis, i.e., amount of actives, unless otherwise indicated.

As used herein, the transitional term “comprising”, which is synonymouswith “including”, “containing”, or “characterized by”, is inclusive oropen-ended and does not exclude additional, un-recited elements ormethod steps. However, in each recitation of “comprising” herein, it isintended that the term also encompass, as alternative embodiments, thephrases “consisting essentially of” and “consisting of”, where“consisting of” excludes any element or step not specified and“consisting essentially of” permits the inclusion of additionalun-recited elements or steps that do not materially affect the basic,essential and novel characteristics of the composition or method underconsideration. In addition, as used herein, the phrase “substantiallyfree of” means that the composition or component may include trace orcontaminant amounts of a material, but that such materials are not addedin functional amounts.

As used herein the expression “compression ignited internal combustionengine” is intended to encompass internal combustion engines that has atleast in part compression ignition. As a result the disclosed technologyis intended to encompass a method of lubricating a compression ignitedinternal combustion engine, as well as spark assisted compressionignited internal combustion engines.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about”. Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention maybe used together with ranges or amounts for any of the other elements.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude: hydrocarbon substituents, including aliphatic, alicyclic, andaromatic substituents; substituted hydrocarbon substituents, that is,substituents containing non-hydrocarbon groups which, in the context ofthis invention, do not alter the predominantly hydrocarbon nature of thesubstituent; and hetero substituents, that is, substituents whichsimilarly have a predominantly hydrocarbon character but contain otherthan carbon in a ring or chain. A more detailed definition of the term“hydrocarbyl substituent” or “hydrocarbyl group” is described inparagraphs [0118] to [0119] of International Publication WO2008147704,or a similar definition in paragraphs [0137] to [0141] of publishedapplication US 2010-0197536.

As described hereinafter the number average molecular weight of thedispersant viscosity modifier and viscosity modifier has been determinedusing known methods, such as GPC analysis using polystyrene standards.Methods for determining molecular weights of polymers are well known.The methods are described for instance: (i) P. J. Flory, “Principles ofPolymer Chemistry”, Cornell University Press 91953), Chapter VII, pp266-315; or (ii) “Macromolecules, an Introduction to Polymer Science”,F. A. Bovey and F. H. Winslow, Editors, Academic Press (1979), pp296-312.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

1. A low viscosity lubricating composition, comprising: a) an oil oflubricating viscosity; b) one or more metal-containing sulfur-freealkyl-phenol based detergents derived from an alkylphenol in an amountto deliver at least 0.2 weight percent alkylphenol-containing soap tothe composition; c) one or more alkaline earth metal sulfonatedetergents in an amount to deliver at least 0.8% by weight sulfonatesoap to the composition; and d) 1 wt % to 4.5 wt % of one or morepolyisobutylene succinimide dispersants; e) 0.1 wt % to 1.2 wt % of adispersant viscosity modifier derived from a polyolefin having a numberaverage molecular weight of at least 20,000; wherein the lubricatingcomposition contains less than 0.2 wt % of a sulfur-coupled phenatedetergent.
 2. The composition of claim 1 wherein the lubricatingcomposition contains less than 0.15 wt % of a sulfur-coupled phenatedetergent.
 3. The composition of claim 2 wherein the composition issubstantially free of sulfur-coupled phenate detergents.
 5. Thecomposition of claim 1 wherein the dispersant viscosity modifiercomprises a mixture of at least one low molecular weight dispersantviscosity modifier, derived from a polyolefin having a number averagemolecular weight of less than 20,000, and at least one high molecularweight dispersant viscosity modifier, derived from a polyolefin having anumber average molecular weight of at least 40,000.
 6. The compositionof claim 5 wherein the at least one low molecular weight dispersantviscosity modifier is derived from a polyolefin having a number averagemolecular weight of 10,000 or lower.
 7. The composition of claim 5wherein the at least one high molecular weight dispersant viscositymodifier is derived from a polyolefin having a number average molecularweight of at least 45,000.
 8. The composition of claim 1 wherein thesulfur-free alkylphenol-based detergent is selected from alkylenecoupled alkylphenol detergents, alkyl salicylate detergents, andcombinations thereof.
 9. The composition of claim 8 wherein thesulfur-free alkylphenol-based detergent comprises Mg saligenin.
 10. Thecomposition of claim 8 wherein the sulfur-free alkylphenol-baseddetergent comprises Ca salixarate.
 11. The composition of claim 1further comprising: a metal dialkyl dithiophosphate, wherein about 65mol % of the alkyl groups have 5 or more carbon atoms, present in anamount to deliver 0.01 to 0.08 weight percent phosphorus to thecomposition.
 12. The composition of claim 1 further comprising: a metaldialkyl dithiophosphate, wherein about 75 mol % of the alkyl groups have5 or more carbon atoms, present in an amount to deliver 0.01 to 0.08weight percent phosphorus to the composition and wherein the compositioncomprises 1 wt % to 4 wt % of one or more polyisobutylene succinimidedispersants.
 13. The composition of claim 1 wherein the lubricatingcomposition is a high temperature high shear fluid having a dynamicviscosity of less than 3.05 at 150° C.
 14. The composition of claim 1wherein the lubricating composition has a viscosity of 10 centistokes orlower at 100° C.
 15. A method of lubricating a compression ignitioninternal combustion engine comprising supplying to the engine a lowphosphorus lubricant composition comprising: a) an oil of lubricatingviscosity; b) one or more metal-containing sulfur-free alkyl-phenolbased detergents in an amount to deliver at least 0.2 weight percentalkylphenol-containing soap to the composition; c) one or more alkalineearth metal sulfonate detergents in an amount to deliver at least 0.8%by weight sulfonate soap to the composition; d) 1 wt % to 4.5 wt % ofone or more polyisobutylene succinimide dispersants; e) 0.1 wt % to 1.2wt % of a dispersant viscosity modifier derived from polyolefin having anumber average molecular weight of at least 20,000; wherein thecomposition contains less than 0.2 weight percent of a sulfur-coupledphenate detergent.
 16. The method of claim 15 wherein the lubricatingcomposition comprises less than 0.15 wt % of a sulfur-coupled phenatedetergent.
 17. The method of claim 15 wherein the dispersant viscositymodifier comprises a mixture of at least one low molecular weightdispersant viscosity modifier, derived from a polyolefin having a numberaverage molecular weight less than 20,000, and at least one highmolecular weight dispersant viscosity modifier, derived from apolyolefin having a number average molecular weight of at least 40,000.18. The method of claim 17 wherein the at least one low molecular weightdispersant viscosity modifier is derived from a polyolefin having anumber average molecular weight of 10,000 or lower.
 19. The method ofclaim 18 wherein the at least one high molecular weight dispersantviscosity modifier is derived from a polyolefin having a number averagemolecular weight of at least 45,000.
 20. The method of claim 15 whereinthe sulfur-free alkylphenol-based detergent is selected from alkylenecoupled alkylphenol detergents, alkylsalicylate detergents, andcombinations thereof.
 21. The method of claim 20 wherein the sulfur-freealkylphenol-based detergent comprises Mg saligenin.
 22. The method ofclaim 20 wherein the sulfur-free alkylphenol-based detergent comprisesCa salixarate.
 23. The method of claim 15 further comprising: a metaldialkyl dithiophosphate, wherein at least about 65 mol % of the alkylgroups have 5 or more carbon atoms, present in an amount to deliver 0.01to 0.08 weight percent phosphorus to the composition.
 24. The method ofclaim 15 further comprising: a metal dialkyl dithiophosphate, wherein atleast about 75 mol % of the alkyl groups have 5 or more carbon atoms,present in an amount to deliver 0.01 to 0.08 weight percent phosphorusto the composition and wherein the composition comprises 1 wt % to 4 wt% of one or more polyisobutylene succinimide dispersants.
 25. The methodof claim 15 wherein the lubricating composition is a high temperaturehigh shear fluid having a dynamic viscosity of less than 3.05 at 150° C.26. The method of claim 15 wherein the lubricating composition has aviscosity of 10 centistokes or lower at 100° C.
 27. A method of reducingadhesive wear in a compression engine lubricated with a low phosphoruslubricant composition, comprising supplying to the engine a lubricantcomposition comprising: a) an oil of lubricating viscosity; b) one ormore metal-containing sulfur-free detergents derived from an alkylphenolin an amount to deliver at least 0.2 weight percentalkylphenol-containing soap to the composition; c) one or more alkalineearth metal sulfonate detergents in an amount to deliver at least 0.8%by weight sulfonate soap to the composition; d) 1 wt % to 4.5 wt % ofone or more polyisobutylene succinimide dispersants; and e) 0.1 wt % to1.2 wt % of a dispersant viscosity modifier derived from polyolefinhaving a number average molecular weight of at least 20,000; wherein thelubricant composition contains less than 0.2 weight percent of asulfur-coupled phenate detergent.
 28. The method of claim 27 wherein thelubricating composition comprises less than 0.15 wt % of asulfur-coupled phenate detergent.
 29. The method of claim 27 wherein thedispersant viscosity modifier comprises a mixture of at least one lowmolecular weight dispersant viscosity modifier, derived from apolyolefin having a number average molecular weight of less than 20,000,and at least one high molecular weight dispersant viscosity modifier,derived from a polyolefin having a number average molecular weight of atleast 40,000.
 30. The method of claim 29 wherein the at least one lowmolecular weight dispersant viscosity modifier is derived from apolyolefin having a number average molecular weight of 10,000 or lower.31. The method of claim 29 wherein the at least one high molecularweight dispersant viscosity modifier is derived from a polyolefin havinga number average molecular weight of at least 45,000.
 32. The method ofclaim 27 wherein the sulfur-free alkylphenol-based detergent is selectedfrom alkylene coupled alkylphenol detergents, alkylsalicylatedetergents, and combinations thereof.
 33. The method of claim 32 whereinthe sulfur-free alkylphenol-based detergent comprises Mg saligenin. 34.The method of claim 32 wherein the sulfur-free alkylphenol-baseddetergent comprises Ca salixarate.
 35. The method of claim 27 furthercomprising: a metal dialkyl dithiophosphate, wherein at least about 65mol % of the alkyl groups have 5 or more carbon atoms, present in anamount to deliver 0.01 to 0.08 weight percent phosphorus to thecomposition.
 36. The method of claim 27 further comprising: a metaldialkyl dithiophosphate, wherein at least about 75 mol % of the alkylgroups have 5 or more carbon atoms, present in an amount to deliver 0.01to 0.08 weight percent phosphorus to the composition and wherein thecomposition comprises 1 wt % to 4 wt % of one or more polyisobutylenesuccinimide dispersants.
 37. The method of claim 27 wherein thelubricating composition is a high temperature high shear fluid having adynamic viscosity of less than 3.05 at 150° C.
 38. The method of claim27 wherein the lubricating composition has a viscosity of 10 centistokesor lower at 100° C.